CN105295958B - Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element - Google Patents

Abstract

The invention provides a liquid crystal alignment agent capable of forming a liquid crystal alignment film with good ultraviolet reliability, a liquid crystal alignment film and a liquid crystal display element with the liquid crystal alignment film. The liquid crystal aligning agent comprises a polymer (A) and a solvent (B). The polymer (A) is obtained by reacting a mixture comprising a tetracarboxylic dianhydride component (a) and a diamine component (b). The diamine component (b) includes a diamine compound (b-1) represented by formula (1), a diamine compound (b-2) represented by formula (2), and a diamine compound (b-3) having a structure represented by formula (3).

Description

Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element

technical field

The present invention relates to a liquid crystal alignment agent (liquid crystal alignment agent), a liquid crystal alignment film (liquid crystal alignment film) and a liquid crystal display element, in particular to a liquid crystal that can form a liquid crystal alignment film with good ultraviolet reliability An alignment agent, a liquid crystal alignment film formed from the above-mentioned liquid crystal alignment agent, and a liquid crystal display element having the above-mentioned liquid crystal alignment film.

Background technique

Liquid crystal displays are widely used in televisions and various monitors. As the LCD display element, there are known LCD display elements having the following liquid crystal cells: Twisted Nematic (TN) type, Super Twisted Nematic (STN) type, In Plane Switching (In Plane Switching, IPS) type, fringe field switching (FFS) type in which the luminance is improved by changing the electrode structure of the IPS type, etc., by increasing the aperture ratio of the display element portion.

As a method for aligning the liquid crystals of these liquid crystal cells, the following method is known: forming an organic film such as a liquid crystal alignment film on the substrate surface, and rubbing (rubbing) the organic film in a certain direction with a cloth such as rayon (rayon). The surface of the film; evaporating silicon oxide obliquely on the surface of the substrate; using the LB method (Langmuir-Blodgett) to form a monomolecular film with a long-chain alkyl group, etc. Among them, from the viewpoint of substrate size, alignment uniformity of liquid crystal, processing time, and processing cost, rubbing processing is most commonly used.

However, if the alignment of the liquid crystal is carried out by rubbing, the dust or static electricity generated during the process may cause the dust to adhere to the surface of the alignment film, resulting in poor display. Especially for substrates with thin film transistor (Thin Film Transistor, TFT) components, the static electricity generated will damage the circuits of the TFT components, resulting in reduced yield. Furthermore, in liquid crystal display elements that will become increasingly finer in the future, as the density of pixels increases, unevenness will be generated on the surface of the substrate, so it tends to be difficult to uniformly perform rubbing treatment.

Therefore, in order to avoid the occurrence of the above-mentioned problems, there is known a photo-alignment method for imparting alignment ability to liquid crystals by irradiating polarized or non-polarized radiation to a photosensitive film (eg, Japanese Patent Laid-Open No. 2005-037654). This document proposes a liquid crystal alignment agent having a repeating unit of conjugated enone and an imide structure. Thereby, static electricity and dust will not be generated, and uniform liquid crystal alignment can be realized. In addition, this method can precisely control the liquid crystal alignment direction in any direction compared with the rubbing treatment. Furthermore, by using a photomask or the like when irradiating radiation, a plurality of regions having different liquid crystal alignment directions can be arbitrarily formed on one substrate.

However, the liquid crystal alignment film has the problem of poor UV reliability. Specifically, after the liquid crystal alignment film is irradiated with ultraviolet rays for a period of time, the voltage retention rate of the liquid crystal display will drop significantly, which will cause problems such as a decrease in the contrast of the liquid crystal display.

Therefore, how to provide a liquid crystal alignment agent capable of forming a liquid crystal alignment film with good ultraviolet reliability, so that when the liquid crystal alignment film formed is applied to a liquid crystal display element, it can still maintain a high voltage retention rate under long-term ultraviolet irradiation , is actually a problem that those skilled in the art want to solve urgently.

Contents of the invention

In view of this, the present invention provides a liquid crystal alignment agent capable of forming a liquid crystal alignment film with good ultraviolet reliability, a liquid crystal alignment film formed of the above liquid crystal alignment agent, and a liquid crystal display element having the above liquid crystal alignment film.

The present invention provides a liquid crystal alignment agent, which includes a polymer (A) and a solvent (B). The polymer (A) is obtained by reacting a mixture including tetracarboxylic dianhydride component (a) and diamine component (b). The diamine component (b) includes a diamine compound (b-1) represented by formula (1), a diamine compound (b-2) represented by formula (2) and a compound having a structure represented by formula (3) Diamine compound (b-3).

Specifically, the diamine compound (b-1) represented by formula (1) is as follows.

In formula (1), Y ¹ represents an alkylene group having a carbon number of 1 to 12; Y ² represents a group having a steroid (cholesterol, steroid) skeleton or a group represented by formula (1-1).

The group represented by formula (1-1) is as follows.

In formula (1-1), R ¹ each independently represents a fluorine atom or a methyl group; R ² represents a hydrogen atom, a fluorine atom, an alkyl group with 1 to 12 carbons, a fluoroalkyl group with 1 to 12 carbons, a carbon Alkoxy group with a number of 1 to 12, -OCH ₂ F, -OCHF ₂ or -OCF ₃ ; Z ¹ , Z ² and Z ³ each independently represent a single bond, an alkylene group with a carbon number of 1 to 3, -O -, Z ⁴ are independently indicated R ^a and R ^b each independently represent a fluorine atom or a methyl group, h and i each independently represent 0, 1 or 2; a represents 0, 1 or 2; b, c and d each independently represent an integer from 0 to 4; e, f and g each independently represent an integer of 0 to 3, and e+f+g≧1.

In addition, the diamine compound (b-2) represented by formula (2) is as follows.

In formula (2), Y ³ each independently represents -O-, -NH-, -CH ₂ O-, Y ⁴ each independently represent a single bond, a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group with a carbon number of 1 to 20; Y ⁵ each independently represent a single bond, -O-, -NH-, wherein m represents an integer from 1 to 5; Y ⁶ each independently represent a nitrogen-containing aromatic heterocyclic group; j represents an integer from 1 to 4.

The structure represented by formula (3) is shown below.

In formula (3), R ³ and R ⁴ each independently represent an alkyl group with a carbon number of 1 to 6, an alkoxy group with a carbon number of 1 to 6, a halogen atom or a cyano group; n1 and n2 independently represent 0 to 4 An integer; n3 represents an integer of 0 or 1; * each independently represents a bonding position.

In one embodiment of the present invention, in the above-mentioned formula (2), Y ³ each independently represent -O-, -NH-, -CH ₂ O-,

In one embodiment of the present invention, in the above formula (2), Y ⁴ each independently represent a single bond, an alkylene group or a phenylene group having 1 to 5 carbon atoms.

In one embodiment of the present invention, in the above formula (2), Y ⁵ each independently represent a single bond, -O-, wherein m represents an integer of 1 to 5.

In one embodiment of the present invention, in the above-mentioned formula (2), Y ⁶ each independently represent pyrrolyl (pyrrolyl), imidazolyl (imidazolyl), pyrazolyl (pyrazolyl), pyridyl (pyridyl) or pyrimidinyl ( pyrimidinyl).

In an embodiment of the present invention, in the above formula (2), j represents an integer from 1 to 3.

In one embodiment of the present invention, the above-mentioned diamine compound (b-3) has at least one member selected from the group consisting of structures represented by formula (3-1) and structures represented by formula (3-2). kind. Specifically, the structure represented by formula (3-1) and the structure represented by formula (3-2) are as follows.

In formula (3-1) and formula (3-2), R ³ and R ⁴ each independently represent an alkyl group with a carbon number of 1 to 6, an alkoxy group with a carbon number of 1 to 6, a halogen atom or a cyano group; R ⁵ and R ⁶ each independently represent an alkyl group with a carbon number of 1 to 40 or an alkyl group with a carbon number of 1 to 40 substituted by a fluorine atom; W ¹ , W ² and W ³ each independently represent -O-, Wherein R ⁷ represents a hydrogen atom or an alkyl group with a carbon number of 1 to 4; X ¹ and X ² each independently represent a methylene group, an aryl group, a divalent alicyclic group, -Si(CH ₃ ) ₂ -, -CH =CH-, -C≡C-, substituted methylene group, substituted aryl group, substituted divalent alicyclic group, substituted -Si(CH ₃ ) ₂ -, substituted -CH=CH- of the substituent, wherein the substituent is a cyano group, a halogen atom or an alkyl group with a carbon number of 1 to 4; n1 and n2 each independently represent an integer of 0 to 4; n3 represents an integer of 0 or 1 ; n4 and n7 each independently represent an integer from 1 to 6; n5 and n8 each independently represent an integer from 0 to 2; n6 represents 0 or 1; * each independently represents a bonding position.

In one embodiment of the present invention, based on the above diamine component (b) being used in an amount of 100 moles, the amount of the diamine compound (b-1) represented by the formula (1) is 0.3 moles to 10 moles, the use amount of the diamine compound (b-2) represented by the formula (2) is 0.3 moles to 10 moles, the diamine compound (b-3) having the structure represented by the formula (3) The amount used is from 5 moles to 90 moles.

The present invention further provides a liquid crystal alignment film formed from the above-mentioned liquid crystal alignment agent.

The present invention further provides a liquid crystal display element, which includes the above-mentioned liquid crystal alignment film.

Based on the above, the liquid crystal alignment film formed by the liquid crystal alignment agent of the present invention has good ultraviolet reliability and is suitable for liquid crystal display elements.

In order to make the above-mentioned features and advantages of the present invention more comprehensible, the following specific embodiments are described in detail together with the accompanying drawings.

Description of drawings

FIG. 1 is a side view of a liquid crystal display element according to an embodiment of the present invention.

Symbol Description

100: liquid crystal display element

110: Unit 1

112: First substrate

114: first conductive film

116: The first liquid crystal alignment film

120: Unit Two

122: Second substrate

124: Second conductive film

126: Second liquid crystal alignment film

130: LCD unit

detailed description

<Liquid crystal alignment agent>

The present invention provides a liquid crystal alignment agent, which includes a polymer (A) and a solvent (B). In addition, the liquid crystal alignment agent may further include an additive (C) if necessary.

Each component of the liquid crystal alignment agent used in the present invention will be described in detail below.

It is explained here that (meth)acrylic acid is used to represent acrylic acid and/or methacrylic acid, and (meth)acrylate is used to represent acrylate and/or methacrylate; similarly, (meth) Acryloyl represents acryloyl and/or methacryloyl.

Polymer (A)

The polymer (A) is obtained by reacting a mixture including tetracarboxylic dianhydride component (a) and diamine component (b).

Tetracarboxylic dianhydride component (a)

Tetracarboxylic dianhydride component (a) comprises aliphatic tetracarboxylic dianhydride compound, alicyclic tetracarboxylic dianhydride compound, aromatic tetracarboxylic dianhydride compound, from formula (I-1) to formula (I - At least one of the tetracarboxylic dianhydride compounds represented by -6), or a combination of the above-mentioned compounds.

Specific examples of the aliphatic tetracarboxylic dianhydride compound may include, but are not limited to, ethanetetracarboxylic dianhydride, butane tetracarboxylic dianhydride, or combinations of the above compounds.

Specific examples of alicyclic tetracarboxylic dianhydride compounds may include, but are not limited to, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4- Cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclobutane Butane tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic Acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride, cis-3,7-dibutylcycloheptane -1,5-diene-1,2,5,6-tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, bicyclo[2.2.2]-octyl-7- Alkene-2,3,5,6-tetracarboxylic dianhydride or a combination of the above compounds.

Specific examples of aromatic tetracarboxylic dianhydride compounds may include, but are not limited to, 3,4-dicarboxy-1,2,3,4-tetrahydronaphthalene-1-succinic dianhydride, pyromellitic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenylsulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic Acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3'-4,4'-diphenylethanetetracarboxylic dianhydride, 3,3',4,4'- Dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3',4,4'-tetraphenylsilane tetracarboxylic dianhydride, 1,2,3,4-furan tetracarboxylic dianhydride, 4, 4'-bis(3,4-dicarboxyphenoxy)diphenylsulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylsulfone dianhydride, 4,4'- Bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride (4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride), 3,3',4,4'-perfluoroiso Propyl diphthalic dianhydride, 3,3',4,4'-diphenyltetracarboxylic dianhydride, bis(phthalic acid)phenylphosphine oxide dianhydride, p-phenylene-bis(tri Phenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenylether dianhydride, bis (Triphenylphthalic acid)-4,4'-diphenylmethane dianhydride, ethylene glycol-bis(anhydrotrimellitate), propylene glycol-bis(anhydrotrimellitate), 1,4 -Butanediol-bis(anhydrotrimellitate), 1,6-Hexanediol-bis(anhydrotrimellitate), 1,8-octanediol-bis(anhydrotrimellitate) , 2,2-bis(4-hydroxyphenyl)propane-bis(dehydrated trimellitate), 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 1,3,3a,4,5, 9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furyl)-naphtho[1,2-c]-furan-1,3-dione {(1,3, 3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-c]furan-1,3-dione)}, 1,3,3a,4 ,5,9b-Hexahydro-5-methyl-5-(tetrahydro-2,5-dioxo-3-furyl)-naphtho[1,2-c]-furan-1,3- Diketone, 1,3,3a,4,5,9b-hexahydro-5-ethyl-5-(tetrahydro-2,5-dipentoxy-3-furyl)-naphtho[1,2 -c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-7-methyl-5-(tetrahydro-2,5-dioxo-3- Furyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-7-ethyl-5-(tetrahydro-2 ,5-Dioxo-3-furyl)-naphtho[ 1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo -3-furyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-ethyl-5-(tetra Hydrogen-2,5-dioxo-3-furyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro -5,8-Dimethyl-5-(tetrahydro-2,5-dioxo-3-furyl)-naphtho[1,2-c]-furan-1,3-dione, 5 -Aromatic tetracarboxylic dianhydride compounds such as (2,5-dipentoxytetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride or combinations of the above-mentioned compounds.

The tetracarboxylic dianhydride compounds represented by formula (I-1) to formula (I-6) are shown below.

In formula (I-5), A ₁ represents a divalent group containing an aromatic ring; r represents an integer from 1 to 2; A ₂ and A ₃ may be the same or different, and may each independently represent a hydrogen atom or an alkyl group. Specific examples of the tetracarboxylic dianhydride compound represented by formula (I-5) include at least one of the compounds represented by formula (I-5-1) to formula (I-5-3).

In formula (I-6), A ₄ represents a divalent group containing an aromatic ring; A ₅ and A ₆ may be the same or different, and each independently represents a hydrogen atom or an alkyl group. The tetracarboxylic dianhydride compound represented by formula (I-6) is preferably a compound represented by formula (I-6-1).

The tetracarboxylic dianhydride component (a) can be used individually or in combination of several types.

Diamine component (b)

The diamine component (b) includes a diamine compound (b-1), a diamine compound (b-2) and a diamine compound (b-3). In addition, in addition to the diamine compound (b-1), diamine compound (b-2) and diamine compound (b-3), the diamine component (b) may further include a diamine compound (b-4) .

Diamine compound (b-1)

The diamine compound (b-1) is a compound represented by formula (1).

In formula (1), Y ¹ represents an alkylene group having a carbon number of 1 to 12; Y ² represents a group having a steroid (cholesterol, steroid) skeleton or a group represented by formula (1-1).

The group represented by formula (1-1) is as follows.

In formula (1-1), R ¹ each independently represents a fluorine atom or a methyl group; R ² represents a hydrogen atom, a fluorine atom, an alkyl group with 1 to 12 carbons, a fluoroalkyl group with 1 to 12 carbons, a carbon Alkoxy, -OCH2F, -OCHF2 or -OCF3 with a number of 1 to 12; Z ¹ , Z ² and Z ³ each independently represent a single bond, an alkylene group with a carbon number of 1 to 3, -O-, Z ⁴ are independently indicated R ^a and R ^b each independently represent a fluorine atom or a methyl group, h and i each independently represent 0, 1 or 2; a represents 0, 1 or 2; b, c and d each independently represent an integer from 0 to 4; e, f and g each independently represent an integer of 0 to 3, and e+f+g≧1.

Specific examples of the diamine compound (b-1) include at least one of the compounds represented by formula (1-2) to formula (1-19).

The diamine compound (b-1) can be produced by a general organic synthesis method. For example, the compounds represented by formula (1-2) to formula (1-19) can be added maleic anhydride to the compound having a steroid skeleton or the compound represented by formula (1-20) respectively, In the presence of potassium, a dinitrobenzoyl chloride compound is added for esterification. Then, a suitable reducing agent such as tin chloride is added to perform a reduction reaction to synthesize a diamine compound (b-1).

In formula (1-20), the definitions of R ¹ , R ² , Z ¹ , Z ² , Z ³ , Z ⁴ , a, b, c, d, e, f and g are the same as in formula (1-1) The definitions of R ¹ , R ² , Z ¹ , Z ² , Z ³ , Z ⁴ , a, b, c, d, e, f and g are the same, and will not be repeated here.

The compound represented by formula (1-20) can be synthesized by methods such as Grignard reaction or Friedal-Crafts acylation reaction (Friedal-Crafts acylation reaction) which are generally used in the synthesis of liquid crystal compounds. .

Based on the usage amount of diamine component (b) being 100 moles, the usage amount of diamine compound (b-1) can be 0.3 moles to 10 moles, preferably 0.4 moles to 8 moles, and more preferably 0.5 moles to 5 moles.

Diamine compound (b-2)

The diamine compound (b-2) is a compound represented by formula (2).

^Y3 each independently represents -O-, -NH-, -CH ₂ O-, Y ⁴ each independently represent a single bond, a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group with a carbon number of 1 to 20; Y ⁵ each independently represent a single bond, -O-, -NH-, wherein m represents an integer from 1 to 5; Y ⁶ each independently represent a nitrogen-containing aromatic heterocyclic group; j represents an integer from 1 to 4.

Specifically, the bonding positions of the two amine groups (—NH ₂ ) in formula (2) are not particularly limited. Specifically, relative to the bonding group (Y ³ ) of the side chain, the two amino groups on the benzene ring are respectively 2,3 positions, 2,4 positions, 2,5 positions, 2,6 positions, 3,4 positions position or 3,5 position etc. Among them, from the viewpoint of reactivity at the time of polyamic acid synthesis, the bonding positions of the two amine groups are preferably 2,4 positions, 2,5 positions, or 3,5 positions. On the other hand, in consideration of the ease of synthesizing the diamine compound, the bonding positions of the two amine groups are more preferably 2,4 positions or 2,5 positions.

In formula (2), Y ³ each independently represents -O-, -NH-, -CH ₂ O-, Among them, in terms of the ease of synthesizing diamine compounds, ^Y3 is preferably each independently representing -O-, -NH-, -CH ₂ O-,

In formula (2), Y4 each independently represents a single bond, a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a divalent alicyclic hydrocarbon group, or a divalent aromatic hydrocarbon group. The divalent aliphatic hydrocarbon group having 1 to 20 carbons may be linear or branched, and may have an unsaturated bond, and is preferably a divalent aliphatic hydrocarbon group having 1 to 10 carbons. Specific examples of the alicyclic ring in the divalent alicyclic hydrocarbon group include cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, and cyclodecane ring. Alkane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring , cyclononadecane ring, cycloeicosane ring, tricycloeicosane ring (tricycloeicosane ring), tricyclodocosane ring (tricyclodocosane ring), bicycloheptane ring (bicycloheptane ring), decahydronaphthalene ring ( decahydronaphthalene ring), norbornene ring (norbornene ring) or adamantane ring (adamantanering), etc.

Specific examples of the aromatic ring in the divalent aromatic hydrocarbon group include benzene ring, naphthalene ring, tetrahydronaphthalene ring, azulene ring (azulenering), indene ring (indene ring), fluorene ring (fluorene ring), anthracene ring, phenanthrene ring or Phenalene ring, etc.

Specifically, in formula (2), Y ⁴ preferably each independently represent a single bond, a straight chain or branched alkylene group with 1 to 10 carbons, a straight chained or branched alkylene group with 1 to 10 carbons Alkenyl, straight chain or branched alkynyl group with 1 to 10 carbons, divalent alicyclic hydrocarbon group or divalent aromatic hydrocarbon group, wherein the alicyclic ring is cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, norbornene ring or adamantane ring, and the aromatic ring is benzene ring, naphthalene ring, tetrahydronaphthalene ring, fluorene ring or anthracene ring. Y is more preferably each independently representing a single bond, a straight chain or branched alkylene group with a carbon number of ¹ to 10, a straight chain or branched alkenyl group with a carbon number of 1 to 10, a divalent alicyclic hydrocarbon group or A divalent aromatic hydrocarbon group, wherein the alicyclic ring is a cyclohexane ring, norbornene ring or adamantane ring, and the aromatic ring is a benzene ring, naphthalene ring, fluorene ring or anthracene ring. Even more preferably, Y ⁴ each independently represent a single bond, a straight-chain or branched alkylene group, cyclohexylene group, phenylene group or naphthylene group with 1 to 10 carbon atoms. Y ⁴ is particularly preferably a straight-chain or branched alkylene or phenylene group each independently representing a single bond and having 1 to 5 carbon atoms.

In formula (2), Y ⁵ each independently represents a single bond, -O-, -NH-, wherein m represents an integer of 1 to 5. ^Y5 is preferably each independently representing a single bond, -O-, wherein m represents an integer of 1 to 5.

In formula (2), Y ⁶ each independently represent a nitrogen-containing aromatic heterocyclic group. Specifically, the nitrogen-containing aromatic heterocyclic group is a nitrogen-containing aromatic heterocyclic group containing at least one structure selected from the group consisting of formula (2a), formula (2b) and formula (2c).

In formula (2c), R ³ represents a linear or branched alkylene group having 1 to 5 carbon atoms.

Specific examples of the nitrogen ^- containing aromatic heterocycle in Y include pyrrole ring, imidazole ring, oxazole ring, thiazole ring, and pyrazole ring. , pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine Purine ring, thiadiazole ring, pyridazine ring, triazine ring, pyrazolidine ring, triazole ring, pyr Pyrazine ring, benzimidazole ring, phenanthrolinering, indole ring, quinoxaline ring, benzothiazolering, phenol phenothiazine ring, oxadiazole ring or acridinine ring. Specifically, Y ⁶ preferably each independently represent pyrrolyl, imidazolyl, pyrazolyl, pyridyl, pyrimidinyl, pyridazinyl, triazinyl, triazolyl, pyrazinyl or benzimidazolyl. From the viewpoint of ultraviolet reliability, Y ⁶ is more preferably each independently representing pyrrolyl, imidazolyl, pyrazolyl, pyridyl or pyrimidinyl.

Also, Y ⁵ is preferably bonded to a substituent not adjacent to the formula (2a), formula (2b) and formula (2c) contained in Y ⁶ .

In formula (2), j represents the integer of 1-4. Moreover, it is preferable that j is an integer which shows 1-3 from a reactive viewpoint with a tetracarboxylic dianhydride compound.

The preferred combination of Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and j in formula (2) is: Y ³ is -O-, -NH-, -CH ₂ O- or Y is a straight chain or branched alkylene group with a carbon number of ¹ to 10, a straight chain or branched alkenyl group with a carbon number of 1 to 10, a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group, wherein, The alicyclic ring is cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, norbornene ring or adamantane ring, and the aromatic ring is benzene ring, naphthalene ring, tetrahydronaphthalene ring ring, fluorene ring or anthracene ring; Y ⁵ is a single bond, -O-, -NH-, (m is an integer from 1 to ⁵ ); the nitrogen-containing aromatic heterocycle in Y is pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrimidine ring, Azoline ring, isoquinoline ring, carbazole ring, purine ring, thiadiazole ring, pyridazine ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, diazepam a phenanthrene ring, an indole ring, a quinoxaline ring, a benzothiazole ring, a phenothiazine ring, an oxadiazole ring or an acridine ring; and j is 1 or 2.

A better combination of Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and j in formula (2) is: Y ³ is -O-, -NH-, -CH ₂ O- or Y is a straight chain or branched alkylene group with a carbon number of ¹ to 10, a straight chain or branched alkenyl group with a carbon number of 1 to 10, a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group, wherein, The alicyclic ring is a cyclohexane ring, a norbornene ring or an adamantane ring, and the aromatic ring is a benzene ring, a naphthalene ring, a fluorene ring or an anthracene ring ^; Y is a single bond, -O-, -NH-, (m is an integer from 1 to ⁵ ); Y is pyrrolyl, imidazolyl, pyrazolyl, pyridyl, pyrimidinyl, pyrazolyl, carbazolyl, pyridazinyl, pyrazolyl, triazinyl , pyrazolinyl, triazolyl, pyrazinyl, or benzimidazolyl; and j is 1 or 2.

The preferred combination of Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and j in formula (2) is: Y ³ is -O-, -NH-, Or -CH ₂ O-; Y ⁴ is a linear or branched alkylene or phenylene group with a carbon number of 1 to 5; Y ⁵ is a single bond, -O-, (m is an integer from 1 to ⁵ ); Y is pyrrolyl, imidazolyl, pyrazolyl, pyridyl or pyrimidinyl; and j is 1, 2 or 3.

Specific examples of the diamine compound (b-2) include diamine compounds of combinations of Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and j described in Tables I to VIII.

Table I

Table II

Table III

Table IV

Table V

Table VI

Table VII

Table VIII

The method for producing the diamine compound (b-2) of the present invention is not particularly limited, for example, it can be produced by the following method: first synthesize the dinitro compound represented by formula (2d), then, in catalyst, solvent and hydrogenation The nitro group is reduced to an amine group in the presence of a compound.

In formula (2d), Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and j are respectively synonymous with Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and j in formula (2), and will not be repeated here.

Specific examples of the catalyst are not particularly limited but may include palladium-carbon, platinum dioxide, raneynickel, platinum black, rhodium-alumina, platinum sulfide carbon, or a combination of the above catalysts. Specific examples of the solvent are not particularly limited but may include ethyl acetate, toluene, tetrahydrofuran, dioxane, alcohols, or a combination of the above solvents. Specific examples of the hydride are not particularly limited but may include hydrogen, hydrazine, hydrogen chloride, or a combination of the above compounds.

The dinitro compound represented by formula (2d) is to make Y ⁴ and Y ⁶ bond through Y ⁵ ; then Y ⁴ is synthesized by the method of Y ³ and the benzene ring bond containing dinitro; ^{The benzene} ring of the dinitro group is bonded to ^Y4 via ^Y3 , and then ^Y4 is synthesized by bonding Y6 via Y5.

^Y3 is -O-, -NH-, -CH ₂ O-, These bonding groups can be formed by well-known techniques of organic synthesis.

For example, in the case where Y ³ is -O- or -CH ₂ O-, the dinitro compound represented by formula (2d) can be obtained by combining a halogen derivative containing dinitro with Y ⁴ , Y The hydroxy derivatives of ⁵ and Y ⁶ are obtained by reacting in the presence of a base; or by reacting a hydroxy derivative containing a dinitro group with a halogen-substituted derivative containing Y ⁴ , Y ⁵ and Y ⁶ in the presence of a base And get.

In the case where Y ³ is -NH-, the dinitro compound represented by formula (2d) can be obtained by making a halogen derivative containing dinitro and an amino-substituted derivative containing Y ⁴ , Y ⁵ and Y ⁶ In the presence of alkali derived from the reaction.

In Y ³ for In the case of , the dinitro compound represented by the formula (2d) can be obtained by reacting a hydroxy derivative containing a dinitro group with an acid chloride compound containing Y ⁴ , Y ⁵ and Y ⁶ in the presence of a base And get.

In Y ³ for In the case of , the dinitro compound represented by the formula (2d) can be obtained by reacting an acid chloride compound containing a dinitro group with an amino-substituted compound containing Y ⁴ , Y ⁵ and Y ⁶ in the presence of a base. have to.

In Y ³ for In the case of , the dinitro compound represented by the formula (2d) can be obtained by reacting an amino-substituted compound with a dinitro-containing acid chloride compound containing Y ⁴ , Y ⁵ and Y ⁶ in the presence of a base. have to.

Specific examples of dinitro-containing halogen derivatives and dinitro-containing derivatives include 3,5-dinitrochlorobenzene (3,5-dinitrochlorobenzene), 2,4-dinitrochlorobenzene (2,4 -dinitrochlorobenzene), 2,4-dinitrofluorobenzene (2,4-dinitrofluorobenzene), 3,5-dinitrobenzoyl chloride (3,5-dinitrobenzoylchloride), 3,5-dinitrobenzoic acid (3,5-dinitrobenzoic acid), 2,4-dinitrobenzoyl chloride (2,4-dinitrobenzoyl chloride), 2,4-dinitrobenzoic acid (2,4-dinitrobenzoic acid), 3,5- Dinitrobenzyl chloride (3,5-dinitrobenzyl chloride), 2,4-dinitrobenzyl chloride (2,4-dinitrobenzylchloride), 3,5-dinitrobenzyl alcohol (3,5-dinitrobenzyl alcohol ), 2,4-dinitrobenzyl alcohol (2,4-dinitrobenzyl alcohol), 2,4-dinitroaniline (2,4-dinitroaniline), 3,5-dinitroaniline (3,5-dinitroaniline ), 2,6-dinitroaniline (2,6-dinitroaniline), 2,4-dinitrophenol (2,4-dinitrophenol), 2,5-dinitrophenol (2,5-dinitrophenol), 2,6-dinitrophenol or 2,4-dinitrophenylacetic acid. The dinitro group-containing halogen derivatives and dinitro group-containing derivatives can be used alone or in combination, from the viewpoint of availability of raw materials and reactivity.

Based on the usage amount of diamine component (b) being 100 moles, the usage amount of diamine compound (b-2) can be 0.3 moles to 10 moles, preferably 0.4 moles to 8 moles, and more preferably 0.5 moles to 5 moles.

In addition, when the diamine compound (b-2) contains pyrrolyl, imidazolyl, pyrazolyl, pyridyl or pyrimidyl, the UV reliability of the formed liquid crystal alignment film can be further improved.

Diamine compound (b-3)

The diamine compound (b-3) has a structure represented by formula (3).

In formula (3), R ³ and R ⁴ each independently represent an alkyl group with a carbon number of 1 to 6, an alkoxy group with a carbon number of 1 to 6, a halogen atom or a cyano group; n1 and n2 independently represent 0 to 4 An integer; n3 represents an integer of 0 or 1; * each independently represents a bonding position.

The diamine compound (b-3) has, for example, at least one selected from the group consisting of the structure represented by formula (3-1) and the structure represented by formula (3-2).

In formula (3-1) and formula (3-2), R ³ and R ⁴ each independently represent an alkyl group with a carbon number of 1 to 6, an alkoxy group with a carbon number of 1 to 6, a halogen atom or a cyano group; R ⁵ and R ⁶ each independently represent an alkyl group with a carbon number of 1 to 40 or an alkyl group with a carbon number of 1 to 40 substituted by a fluorine atom; W ¹ , W ² and W ³ each independently represent -O-, Wherein R ⁷ represents a hydrogen atom or an alkyl group with a carbon number of 1 to 4; X ¹ and X ² each independently represent a methylene group, an aryl group, a divalent alicyclic group, -Si(CH ₃ ) ₂ -, -CH =CH-, -C≡C-, substituted methylene group, substituted aryl group, substituted divalent alicyclic group, substituted -Si(CH ₃ ) ₂ -, substituted -CH=CH- of the substituent, wherein the substituent is a cyano group, a halogen atom or an alkyl group with a carbon number of 1 to 4; n1 and n2 each independently represent an integer of 0 to 4; n3 represents an integer of 0 or 1 ; n4 and n7 each independently represent an integer from 1 to 6; n5 and n8 each independently represent an integer from 0 to 2; n6 represents 0 or 1; * each independently represents a bonding position.

In formula (3-1) and formula (3-2), specific examples of the alkyl group having a carbon number of 1 to 40 may include n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl base, n-lauryl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-decyl Nonalkyl or n-eicosyl, etc. Specific examples of alkyl groups having 1 to 40 carbon atoms substituted by fluorine atoms may include 4,4,4-trifluorobutyl, 4,4,5,5,5-pentafluoropentyl, 4,4,5 ,5,6,6,6-heptafluorohexyl, 3,3,4,4,5,5,5-heptafluoropentyl, 2,2,2-trifluoroethyl, 2,2,3,3 , 3-pentafluoropropyl, 2-(perfluorobutyl)ethyl, 2-(perfluorooctyl)ethyl or 2-(perfluorodecyl)ethyl, etc.

An alkyl group with 1 to 40 carbons substituted by fluorine atoms is an alkyl group with 1 to 40 carbons substituted by fluorine atoms for some or all of the hydrogen atoms, preferably a carbon number with some or all of the hydrogen atoms substituted by fluorine atoms is an alkyl group of 1 to 20.

The alkyl group having 1 to 40 carbon atoms substituted by a fluorine atom is preferably a straight-chain or branched fluoroalkyl group having 1 to 16 carbon atoms, and is capable of exhibiting good liquid crystal alignment. In other words, it is preferably a straight-chain fluoroalkyl group with a carbon number of 1 to 8, more preferably a straight-chain fluoroalkyl group with a carbon number of 3 to 6, such as 2,2,2-trifluoroethyl, 3, 3,3-trifluoro-n-propyl, 4,4,4-trifluoro-n-butyl, 4,4,5,5,5-pentafluoro-n-pentyl or 4,4,5,5,6,6, 6-heptafluorohexyl, etc., and preferably 2,2,2-trifluoroethyl, 3,3,3-trifluoro-n-propyl, 4,4,4-trifluoro-n-butyl or 4,4, 5,5,5-Pentafluoro-n-pentyl.

Specific examples of the diamine compound (b-3) having a structure represented by formula (3-1) include compounds represented by formula (3-1-1) to formula (3-1-25).

Specific examples of the diamine compound (b-3) having a structure represented by formula (3-2) include compounds represented by formula (3-2-1) to formula (3-2-2).

The diamine compound (b-3) is preferably selected from the group represented by formula (3-1-3), formula (3-1-6), formula (3-1-7), formula (3-2-1) at least one of the group consisting of diamine compounds.

Based on the usage amount of diamine component (b) being 100 moles, the usage amount of diamine compound (b-3) can be 5 moles to 90 moles, preferably 8 moles to 85 moles, and more preferably 10 moles to 80 moles. When the polymer (A) in the liquid crystal alignment agent uses diamine compound (b-1), diamine compound (b-2) and diamine compound (b-3) at the same time, the UV reliability of the formed liquid crystal alignment film better.

Diamine compound (b-4)

In addition to the diamine compound (b-1), diamine compound (b-2) and diamine compound (b-3), the diamine component (b) of the present invention can also be selected within the scope of not affecting the efficacy The diamine compound (b-4) is mixed and used selectively. Specific examples of diamine compounds (b-4) include, but are not limited to, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diamine 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diamine decane, 4,4'-diaminoheptane, 1,3-diamino-2,2-dimethylpropane, 1,6-diamino-2,5-dimethylhexane, 1,7-diamino-2,5-dimethylheptane, 1,7-diamino-4,4-dimethylheptane, 1,7-diamino-3-methylheptane , 1,9-diamino-5-methylnonane, 2,11-diaminododecane, 1,12-diaminooctadecane, 1,2-bis(3-aminopropoxy base) ethane, 4,4'-diaminodicyclohexylmethane, 4,4'-diamino-3,3'-dimethyldicyclohexylamine, 1,3-diaminocyclohexane , 1,4-diaminocyclohexane, isophorone diamine, tetrahydrodicyclopentadiene diamine, tricyclic (6.2.1.02,7)-undecene dimethyl diamine, 4 ,4'-methylenebis(cyclohexylamine), 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminobis Phenylsulfone, 4,4'-diaminobenzanilide, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1,5-diamino Naphthalene, 5-amino-1-(4'-aminophenyl)-1,3,3-trimethylhydroindene, 6-amino-1-(4'-aminophenyl)-1, 3,3-trimethylhydroindene, hexahydro-4,7-methylindenyl dimethylenediamine, 3,3'-diaminobenzophenone, 3,4'-diamine benzophenone, 4,4'-diaminobenzophenone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-( 4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)benzene base] sulfone, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy) Benzene, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 9,10-bis(4-aminophenyl)anthracene, 2,7-diaminofluorene, 9,9-bis (4-Aminophenyl)fluorene, 4,4'-methylene-bis(2-chloroaniline), 4,4'-(p-phenyleneisopropylidene)bisaniline, 4,4' -(m-Phenylisopropylidene)bisaniline, 2,2'-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane, 4,4 '-Bis[(4-amino-2-trifluoromethyl)phenoxy]-octafluorobiphenyl, 5-[4-(4-n-pentylcyclohexyl)cyclohexyl]phenyl-methylene Base-1,3-diaminophenyl {5-[4-(4-n-pentylcyclohexyl)cyclohexyl]phenylmethylene-1,3 -diaminobenzene} or 1,1-bis[4-(4-aminophenoxy)phenyl]-4-(4-ethylphenyl)cyclohexane{1,1-bis[4-(4- aminophenoxy)phenyl]-4-(4-ethylphenyl)cyclohexane}, at least one of the diamine compounds represented by formula (II-1) to formula (II-30), or a combination of the above compounds.

The diamine compounds represented by formula (II-1) to formula (II-30) are shown below.

In formula (II-1), B ¹ represents -O-, B represents a group with a steroid skeleton, a trifluoromethyl group, a fluoro group, an alkyl group with a carbon number of ² to 30, or a nitrogen-containing ring structure derived from pyridine, pyrimidine, triazine, piperidine or piperazine. Monovalent group.

Specific examples of compounds represented by formula (II-1) include, but are not limited to, 2,4-diaminophenyl ethyl formate (2,4-diaminophenyl ethyl formate), 3,5-diaminophenyl formic acid ethyl Esters (3,5-diaminophenyl ethylformate), 2,4-diaminophenyl propyl formate (2,4-diaminophenyl propyl formate), 3,5-diaminophenyl propyl formate (3,5-diaminophenyl propyl formate), 1-dodecyloxy-2,4-diaminobenzene (1-dodecoxy-2,4-diaminobenzene), 1-hexadecyloxy-2,4-diaminobenzene (1 -hexadecoxy-2,4-diaminobenzene), 1-octadecyloxy-2,4-diaminobenzene (1-octadecoxy-2,4-diaminobenzene), from formula (II-1-1) to formula ( At least one of the compounds represented by II-1-6), or a combination of the above compounds.

Compounds represented by formula (II-1-1) to formula (II-1-6) are shown below.

In formula (II- ² ), B1 is the same as B1 in formula (II ^{- 1} ), and ^B3 and B4 each independently represent a divalent alicyclic ring, a divalent aromatic ring or a divalent heterocyclic group; B5 represents an alkyl group with a carbon number of ³ to 18, an alkoxy group with a carbon number of 3 to 18, a fluoroalkyl group with a carbon number of 1 to 5, a fluoroalkoxy group with a carbon number of 1 to 5, a cyano group or halogen atom.

Specific examples of the compound represented by formula (II-2) include at least one of the compounds represented by formula (II-2-1) to formula (II-2-13). Specifically, compounds represented by formula (II-2-1) to formula (II-2-13) are shown below.

In formula (II-2-10) to formula (II-2-13), s represents an integer of 3 to 12.

In formula (II- ³ ), B6 each independently represents a hydrogen atom, an acyl group with 1 to 5 carbons, an alkyl group with 1 to 5 carbons, an alkoxy group with 1 to 5 carbons, or a halogen atom, and B ⁶ in each repeating unit may be the same or different; u represents an integer of 1 to 3.

Specific examples of the compound represented by the formula (II-3) include (1) when u is 1: p-diaminobenzene, m-diaminobenzene, o-diaminobenzene or 2,5-diamine (2) When u is 2: 4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, Methyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamine Biphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 2,2',5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2 '-Dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl or 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, etc. or (3) when u is 3: 1,4-bis(4'-aminophenyl)benzene and the like.

Specific examples of the compound represented by formula (II-3) preferably include p-diaminobenzene, 2,5-diaminotoluene, 4,4'-diaminobiphenyl, 3,3'-bis Methoxy-4,4'-diaminobiphenyl, 1,4-bis(4'-aminophenyl)benzene or a combination of the above compounds.

In formula (II-4), v represents an integer of 2 to 12.

In formula (II-5), w represents an integer of 1 to 5. The compound represented by formula (II-5) is preferably 4,4'-diamino-diphenylsulfide.

In formula (II-6), B ⁷ and B ⁹ each independently represent a divalent organic group, and B ⁷ and B ⁹ can be the same or different; B ⁸ represents a group derived from pyridine, pyrimidine, triazine, piperidine or piperidine A divalent group with a ring structure containing a nitrogen atom such as oxazine.

In formula (II-7), B ¹⁰ , B ¹¹ , B ¹² and B ¹³ each independently represent a hydrocarbon group with a carbon number of 1 to 12, and B ¹⁰ , B ¹¹ , B ¹² and B ¹³ may be the same or different; X1 Each independently represents an integer of 1 to 3; X2 represents an integer of 1 to 20.

In formula (II-8), B ¹⁴ represents an oxygen atom or a cyclohexylene group; B ¹⁵ represents a methylene group (methylene, -CH2-); B ¹⁶ represents a phenylene group or a cyclohexylene group; B ¹⁷ represents hydrogen atom or heptyl.

Specific examples of the compound represented by formula (II-8) include a compound represented by formula (II-8-1), a compound represented by formula (II-8-2), or a combination of the above compounds.

Compounds represented by formula (II-9) to formula (II-30) are shown below.

In formula (II-17) to formula (II-25), B ¹⁸ preferably represents an alkyl group with a carbon number of 1 to 10 or an alkoxy group with a carbon number of 1 to 10; B ¹⁹ preferably represents a hydrogen atom , an alkyl group having 1 to 10 carbons or an alkoxy group having 1 to 10 carbons.

Specific examples of diamine compounds (b-4) preferably include, but are not limited to, 1,2-diaminoethane, 4,4'-diaminodicyclohexylmethane, 4,4'-diaminodicyclohexylmethane, 4,4'-diaminobis Phenylmethane, 4,4'-diaminodiphenyl ether, 5-[4-(4-n-pentylcyclohexyl)cyclohexyl]phenylmethylene-1,3-diaminobenzene, 1,1-bis[4-(4-aminophenoxy)phenyl]-4-(4-ethylphenyl)cyclohexane, ethyl 2,4-diaminophenylcarboxylate, by formula A compound represented by (II-1-1), a compound represented by formula (II-1-2), a compound represented by formula (II-1-5), a compound represented by formula (II-2-1), Compounds represented by formula (II-2-11), p-diaminobenzene, m-diaminobenzene, ortho-diaminobenzene, compounds represented by formula (II-8-1), compounds represented by formula (II-26 ), a compound represented by formula (II-29), or a combination of the above compounds.

The above-mentioned diamine compound (b-4) can be used individually or in combination of multiple types.

In the above-mentioned diamine compound (b-4), when the polymer (A) in the liquid crystal alignment agent is used from formula (II-1), formula (II-2), formula (II-26) to formula (II-30 ) represents at least one of the diamine compounds, the ultraviolet reliability of the formed liquid crystal alignment film is particularly good.

Based on the total number of moles of diamine component (b) being 100 moles, the amount of diamine compound (b-4) used can be from 0 to 94 moles, preferably from 10 moles to 92 moles, and more preferably from 20 moles to 89 moles.

Process for preparing polymer (A)

The polymer (A) may include at least one of polyamic acid and polyimide. In addition, the polymer (A) may further include a polyimide-based block copolymer. The preparation methods of the above-mentioned various polymers are further described below.

Method for preparing polyamic acid

The method for preparing polyamic acid is to first dissolve the mixture in a solvent, wherein the mixture includes tetracarboxylic dianhydride component (a) and diamine component (b), and carry out polycondensation at a temperature of 0°C to 100°C reaction. After reacting for 1 hour to 24 hours, the reaction solution is distilled under reduced pressure with an evaporator to obtain polyamic acid. Alternatively, the reaction solution is poured into a large amount of poor solvent to obtain a precipitate. Then, the precipitate is dried under reduced pressure to obtain polyamic acid. In the mixture, based on the total usage amount of the diamine component (b) being 100 moles, the usage amount of the tetracarboxylic dianhydride component (a) is preferably 20 moles to 200 moles, more preferably 30 moles to 120 moles .

The solvent used in the polycondensation reaction may be the same as or different from the solvent in the liquid crystal alignment agent described below, and the solvent used in the polycondensation reaction is not particularly limited as long as it can dissolve the reactants and products. The solvent preferably includes but not limited to (1) aprotic polar solvent, for example: N-methyl-2-pyrrolidinone (N-methyl-2-pyrrolidinone; NMP), N,N-dimethylacetamide, Aprotic polar solvents such as N,N-dimethylformamide, dimethylsulfoxide, γ-butyrolactone, tetramethylurea or hexamethylphosphoric triamine; or (2) phenolic solvents, For example: phenolic solvents such as m-cresol, xylenol, phenol, or halogenated phenols. Based on 100 parts by weight of the total mixture, the solvent used in the polycondensation reaction is preferably used in an amount of 200 to 2000 parts by weight, and more preferably 300 to 1800 parts by weight.

It should be noted that in the polycondensation reaction, the solvent can be used together with an appropriate amount of poor solvent, and the poor solvent will not cause the precipitation of polyamic acid. Poor solvents can be used alone or in combination, and they include but are not limited to (1) alcohols, such as: methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4- Alcohols such as butylene glycol or triethylene glycol; (2) ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.; (3) esters, For example: esters of methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate or ethylene glycol ethyl ether acetate; (4) ethers, such as: diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, or diethylene glycol Ethers such as dimethyl ether; (5) halogenated hydrocarbons, such as dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene or o- Halogenated hydrocarbons such as dichlorobenzene; or (6) hydrocarbons, such as tetrahydrofuran, hexane, heptane, octane, benzene, toluene or xylene or any combination of the above solvents. Based on 100 parts by weight of the diamine component (b), the amount of the poor solvent is preferably 0 to 60 parts by weight, and more preferably 0 to 50 parts by weight.

Method for preparing polyimide

The method for preparing polyimide is obtained by heating the polyamic acid prepared by the above method for preparing polyamic acid in the presence of a dehydrating agent and a catalyst. During the heating process, the amic acid functional group in the polyamic acid can be transformed into an imide functional group through a dehydration ring-closure reaction (ie, imidization).

The solvent used in the dehydration ring-closing reaction can be the same as the solvent (B) in the liquid crystal alignment agent, so it will not be repeated here. Based on 100 parts by weight of the polyamic acid, the amount of the solvent used in the dehydration ring closure reaction is preferably 200 to 2000 parts by weight, and more preferably 300 to 1800 parts by weight.

In order to obtain a better degree of imidization of the polyamic acid, the operating temperature of the dehydration ring closure reaction is preferably from 40°C to 200°C, more preferably from 40°C to 150°C. If the operating temperature of the dehydration ring-closing reaction is lower than 40° C., the imidization reaction will not be complete, and the degree of imidization of the polyamic acid will be reduced. However, if the operating temperature of the dehydration ring-closing reaction is higher than 200° C., the weight average molecular weight of the obtained polyimide is low.

The dehydrating agent used in the dehydration ring-closing reaction can be selected from acid anhydride compounds, for example, acid anhydride compounds such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride. Based on 1 mole of the polyamic acid, the amount of the dehydrating agent is 0.01 mole to 20 mole. The catalyst used in the dehydration ring-closing reaction can be selected from (1) pyridine compounds, such as: pyridine compounds such as pyridine, collidine or lutidine; (2) tertiary amine compounds, such as: three Tertiary amine compounds such as ethylamine. Based on 1 mole of the dehydrating agent, the catalyst can be used in an amount of 0.5 moles to 10 moles.

Method for preparing polyimide-based block copolymers

Polyimide block copolymer is selected from polyamic acid block copolymer, polyimide block copolymer, polyamic acid-polyimide block copolymer or the above-mentioned polymer random combination.

The method for preparing polyimide-based block copolymers is preferably to first dissolve the starting material in a solvent and carry out polycondensation reaction, wherein the starting material includes at least one polyamic acid and/or at least one polyamic acid imide, and may further include a carboxylic acid anhydride component and a diamine component.

The carboxylic acid anhydride component and the diamine component in the starter can be the same as the tetracarboxylic dianhydride component (a) and the diamine component (b) used in the method for preparing polyamic acid, and used for polyamic acid The solvent in the condensation reaction may be the same as the solvent in the liquid crystal alignment agent described below, which will not be repeated here.

Based on 100 parts by weight of the starting material, the solvent used in the polycondensation reaction is preferably used in an amount of 200 to 2000 parts by weight, and more preferably 300 to 1800 parts by weight. The operating temperature of the polycondensation reaction is preferably from 0°C to 200°C, and more preferably from 0°C to 100°C.

The starting material preferably includes but is not limited to (1) two kinds of polyamic acids with different end groups and different structures; (2) two kinds of polyimides with different end groups and different structures; (3) Polyamic acid and polyimide with different terminal groups and different structures; (4) polyamic acid, carboxylic anhydride components and diamine components, wherein at least one of the carboxylic anhydride components and diamine components A structure different from the carboxylic anhydride component and diamine component used to form polyamic acid; (5) polyimide, carboxylic anhydride component and diamine component, wherein the carboxylic anhydride component and diamine component At least one of the amine components is different from the structure of the carboxylic anhydride component and the diamine component used to form the polyimide; (6) polyamic acid, polyimide, carboxylic anhydride component and diamine Components, wherein at least one of the carboxylic anhydride component and the diamine component is different from the structure of the carboxylic anhydride component and the diamine component used to form polyamic acid or polyimide; (7) two (8) Two kinds of polyimides, carboxylic anhydride components and diamine components with different structures; (9) Two kinds of terminal groups Anhydride-based polyamic acid and diamine components with different structures; (10) Two kinds of polyamic acid and carboxylic anhydride components with amine-based end groups and different structures; (11) Two kinds of terminal groups with anhydride groups or (12) two polyimide and carboxylic anhydride components whose end groups are amine groups and have different structures.

The polyamic acid, polyimide, and polyimide-based block copolymers are preferably end-modified polymers that have been first adjusted in molecular weight within the range that does not affect the efficacy of the present invention. By using terminal-modified polymers, the coating performance of the liquid crystal alignment agent can be improved. The method for preparing the end-modified polymer can be obtained by adding monofunctional compounds while the polyamic acid undergoes polycondensation reaction.

Specific examples of monofunctional compounds include but are not limited to (1) monobasic acid anhydrides, such as: maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl anhydride, Monobasic acid anhydrides such as alkyl succinic anhydride or n-hexadecyl succinic anhydride; (2) Monoamine compounds, such as: aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, Monoamine compounds such as n-octadecylamine or n-eicosylamine; or (3) monoisocyanate compounds, such as monoisocyanate compounds such as phenyl isocyanate or naphthyl isocyanate.

solvent (B)

Specific examples of solvent (B) include, but are not limited to, N-methyl-2-pyrrolidone (N-methyl-2-pyrrolidone, NMP), γ-butyrolactone, γ-butyrolactam, 4-hydroxyl-4-methyl -2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxy propionate, ethyl ethoxy propionate, ethylene glycol methyl ether, ethylene glycol ethyl ethylene glycol n-propyl ether, ethylene glycol n-propyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate , diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, two Ethylene glycol monoethyl ether acetate or N,N-dimethylformamide or N,N-dimethylacetamide (N,N-dimethyl acetamide), etc. The solvent (B) can be used individually or in combination of multiple types.

Based on 100 parts by weight of the polymer (A), the used amount of the solvent (B) is 500 to 3000 parts by weight, preferably 800 to 2500 parts by weight, and more preferably 1000 to 2000 parts by weight.

Additive (C)

In the range that does not affect the effectiveness of the present invention, the liquid crystal alignment agent can optionally add additives (C), wherein the additives (C) include compounds with at least two epoxy groups, silane compounds with functional groups, or a combination thereof.

Compounds having at least two epoxy groups include, but are not limited to, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether , Polypropylene Glycol Diglycidyl Ether, Neopentyl Glycol Diglycidyl Ether, 1,6-Hexanediol Diglycidyl Ether, Glycerol Diglycidyl Ether, 2,2-Di Bromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraepoxypropyl-2,4-hexanediol, N,N,N',N'-tetraepoxypropyl- m-Xylylenediamine, 1,3-bis(N,N-diepoxypropylaminomethyl)cyclohexane, N,N,N',N'-tetraepoxypropyl-4,4 '-Diaminodiphenylmethane, N,N-epoxypropyl-p-glycidoxyaniline, 3-(N-allyl-N-epoxypropyl)aminopropyltrimethoxy silane, 3-(N,N-diecidylpropyl)aminopropyltrimethoxysilane, or a combination of the above compounds.

The compound which has at least two epoxy groups mentioned above can be used individually or in combination of several types.

Based on 100 parts by weight of the polymer (A), the compound having at least two epoxy groups may be used in an amount of 0 to 40 parts by weight, and preferably 0.1 to 30 parts by weight.

Specific examples of silane compounds having functional groups include, but are not limited to, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltrimethoxysilane, -Aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyl Methyldimethoxysilane, 3-ureidopropyltrimethoxysilane (3-ureidopropyltrimethoxysilane), 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane Oxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine Ethylenetriamine, 10-trimethoxysilyl-1,4,7-triazidecane, 10-triethoxysilyl-1,4,7-triazidecane, 9-trimethoxysilyl -3,6-diazinonyl acetate, 9-triethoxysilyl-3,6-diazinonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N -Benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis(oxyethylene)-3-aminopropyltrimethoxysilane, N-bis(oxyethylene)-3-aminopropyltriethoxysilane, or a combination of the foregoing. Additives (C) can be used alone or in combination.

Based on 100 parts by weight of the polymer (A), the amount of the silane compound having a functional group may be 0 to 10 parts by weight, and preferably 0.5 to 10 parts by weight.

The additive (C) is preferably used in an amount of 0.5 to 50 parts by weight, and more preferably 1 to 45 parts by weight, based on 100 parts by weight of the total polymer (A).

<Preparation method of liquid crystal alignment agent>

The preparation method of the liquid crystal alignment agent of the present invention is not particularly limited, and can be prepared by a general mixing method. For example, first add the solvent (B) to the polymer (A) prepared in the above manner at a temperature of 0°C to 200°C, and optionally add the additive (C), and finally use a stirring device to continuously Stir until dissolved. It is preferred to carry out the addition of the solvent (B) at a temperature of 20°C to 60°C.

At 25° C., the viscosity of the liquid crystal alignment agent of the present invention is generally 15 cps to 35 cps, preferably 17 cps to 33 cps, more preferably 20 cps to 30 cps.

<Formation Method of Liquid Crystal Alignment Film>

The liquid crystal alignment agent of the present invention can be suitably used to form a liquid crystal alignment film by a photo-alignment method.

The method of forming a liquid crystal alignment film can include, for example, coating a liquid crystal alignment agent on a substrate to form a coating film, and irradiating the coating film with polarized or non-polarized radiation from a direction inclined relative to the coating film surface; A method of imparting liquid crystal alignment ability to the coating film by irradiating the coating film with polarized radiation in a direction perpendicular to the film surface.

First, the liquid crystal alignment agent of the present invention is coated on the substrate provided with a patterned transparent conductive film by an appropriate coating method such as a roll coating method, a spin coating method, a printing method, and an ink-jet method. transparent conductive film side. After coating, the coated surface is subjected to a pre-bake treatment, followed by a post-bake treatment, whereby a coating film is formed. The purpose of the above-mentioned pre-baking treatment is to volatilize the organic solvent in the pre-coating layer. Conditions of the prebaking process are, for example, at 40 to 120° C. for 0.1 to 5 minutes. The post-baking conditions are preferably at 120-300°C, more preferably at 150-250°C, preferably for 5-200 minutes, more preferably for 10-100 minutes. The thickness of the coating film after the post-baking is preferably 0.001-1 μm, and more preferably 0.005-0.5 μm.

The substrate can be made of glass such as float glass, soda lime glass; plastics such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone or polycarbonate, etc. Formed transparent substrates, etc.

As the transparent conductive film, a NESA film made of SnO ₂ , an ITO film made of In ₂ O ₃ —SnO ₂ , or the like can be used. In order to form these transparent conductive film patterns, a photo-etching technique, a method of using a mask when forming a transparent conductive film, or the like can be used.

When coating the liquid crystal alignment agent, in order to improve the adhesion between the substrate or the transparent conductive film and the coating film, functional silane compounds, titanates, etc. can be pre-coated on the substrate and transparent conductive film.

Next, the coating film is irradiated with polarized or non-polarized radiation to impart liquid crystal alignment energy, and a liquid crystal alignment film is formed from the coating film. Here, the radiation can be used, for example, ultraviolet rays including light with a wavelength of 150 to 800 nm and visible light, and preferably ultraviolet rays including light with a wavelength of 300 to 400 nm. When the radiation used is polarized (linearly polarized or partially polarized), it may be irradiated from a direction perpendicular to the coating film surface, or may be irradiated from an oblique direction in order to impart a pretilt angle. On the other hand, when irradiating non-polarized radiation, it is necessary to irradiate from a direction oblique to the coating film surface.

As a light source for irradiating radiation, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, or an excimer laser can be used. The ultraviolet rays in the aforementioned preferable wavelength region can be obtained by a method of using the aforementioned light source in combination with, for example, a filter, a diffraction grating, and the like.

The radiation dose is preferably 1 J/m ² or more and less than 10000 J/m ² , more preferably 10 to 3000 J/m ² . In addition, when imparting liquid crystal alignment energy to a coating film formed of a conventionally known liquid crystal alignment agent by a photo-alignment method, a radiation dose of 10000 J/m ² or more is required. However, if the liquid crystal alignment agent of the present invention is used, even if the radiation dose during the photo-alignment method is 3000 J/m ² or less, further 1000 J/m ² or less, and further 300 J/m ² or less, it can also give good Liquid crystal alignment can help reduce the manufacturing cost of liquid crystal display elements.

<Liquid crystal display element and its manufacturing method>

The liquid crystal display element of the present invention includes a liquid crystal alignment film formed from the liquid crystal alignment agent of the present invention. The liquid crystal display element of the present invention can be produced as follows.

Two substrates on which the liquid crystal alignment film was formed as described above are prepared, and liquid crystal is placed between the two substrates to manufacture a liquid crystal cell. In order to manufacture a liquid crystal cell (cell), the following two methods are mentioned, for example.

The first method: first, two substrates are arranged oppositely across a gap (intercellular gap), so that their respective liquid crystal alignment films face each other; the peripheral parts of the two substrates are bonded together using a sealant; Liquid crystal is injected into the intercellular space divided by the sealant; and the injection hole is closed, so that the liquid crystal cell can be manufactured.

The second method: a method called ODF (One Drop Fill, infusion) method. First of all, on a predetermined position on one of the two substrates forming the liquid crystal alignment film, for example, an ultraviolet curable sealing material is coated; liquid crystal is dropped on the surface of the liquid crystal alignment film; then, the other substrate is bonded to make the liquid crystal alignment film facing each other; next, the entire surface of the substrate is irradiated with ultraviolet rays to cure the sealant, whereby a liquid crystal cell can be manufactured.

In the case of using any of the above methods, it is desirable to heat the liquid crystal cell to the temperature at which the liquid crystal used is in the isotropic phase, and then slowly cool it to room temperature, thereby removing the flow alignment when filling the liquid crystal.

Then, the liquid crystal display element of the present invention can be obtained by bonding a polarizing plate to the outer surface of the liquid crystal cell. Here, when the liquid crystal alignment film is horizontally aligned, by adjusting the angle formed by the polarization direction of the linearly polarized radiation irradiated on the two substrates on which the liquid crystal alignment film is formed and the angle between each substrate and the polarizer, a TN-type Or the liquid crystal display element of the STN type liquid crystal cell. On the other hand, when the liquid crystal alignment film is vertically aligned, by forming a liquid crystal cell, the direction of the easy-to-align axis (easy-to-align axis) of the two substrates on which the liquid crystal alignment film is formed is parallel, and the polarizer and the The liquid crystal cells are pasted together so that the polarization direction and the easy alignment axis form an angle of 45°, and a liquid crystal display element with a vertically aligned liquid crystal cell can be formed.

As the sealing agent, for example, an epoxy resin containing a curing agent and alumina balls as spacers can be used.

Specific examples of liquid crystals include nematic liquid crystals, smectic liquid crystals, and the like.

In the case of TN-type or STN-type liquid crystal cells, preferably a nematic liquid crystal with positive dielectric anisotropy, for example, biphenyl-based liquid crystals (biphenyl-based liquid crystals), phenylcyclohexane liquid crystals ( phenylcyclohexane-based liquid crystal), ester liquid crystal, terphenyl liquid crystal, biphenyl cyclohexane-based liquid crystal, pyrimidine-based liquid crystal, dioxin Dioxane-based liquid crystals, bicyclooctane-based liquid crystals, cubane-based liquid crystals, etc. In addition, cholesteric liquid crystals such as cholesteryl chloride, cholesteryl nonabenzoate, and cholesteryl carbonate can be further added to the aforementioned liquid crystals; Chiral agents sold under the trade names "C-15" and "CB-15" (manufactured by Merck); p-decyloxybenzylidene-p-amino-2-methylbutyl cinnamate (p -decyloxybenzylidene-p-amino-2-methyl butyl cinnamate) and other ferroelectric liquid crystals are used.

On the other hand, in the case of a vertically aligned liquid crystal cell, a nematic liquid crystal having negative dielectric anisotropy is preferable, for example, a dicyanobenzene-based liquid crystal, a pyridazine-based liquid crystal, or a dicyanobenzene-based liquid crystal can be used. (pyridazine-based liquid crystal), Schiff base-based liquid crystal, azoxy-based liquid crystal, biphenyl-based liquid crystal, phenylcyclohexane Liquid crystal (phenylcyclohexane-based liquid crystal), etc.

The polarizing plate used outside the liquid crystal cell includes a polarizing film called "H film" obtained by sandwiching polyvinyl alcohol while stretching and aligning polyvinyl alcohol with protective films of cellulose acetate, and absorbing iodine. A polarizer or a polarizer formed by the H film itself.

The liquid crystal display device of the present invention manufactured in this way has excellent display performance, and the display performance does not deteriorate even if it is used for a long time.

FIG. 1 is a side view of a liquid crystal display element according to an embodiment of the present invention. The liquid crystal display element 100 includes a first unit 110 , a second unit 120 and a liquid crystal unit 130 , wherein the second unit 120 is disposed separately from the first unit 110 , and the liquid crystal unit 130 is disposed between the first unit 110 and the second unit 120 .

The first unit 110 includes a first substrate 112, a first conductive film 114, and a first liquid crystal alignment film 116, wherein the first conductive film 114 is located between the first substrate 112 and the first liquid crystal alignment film 116, and the first liquid crystal alignment film 116 is located on one side of the liquid crystal cell 130 .

The second unit 120 includes a second substrate 122, a second conductive film 124, and a second liquid crystal alignment film 126, wherein the second conductive film 124 is located between the second substrate 122 and the second liquid crystal alignment film 126, and the second liquid crystal alignment film 126 is located on the other side of the liquid crystal cell 130 . In other words, the liquid crystal unit 130 is located between the first liquid crystal alignment film 116 and the second liquid crystal alignment film 126 .

The first substrate 112 and the second substrate 122 are selected from transparent materials, etc., wherein the transparent materials include but not limited to alkali-free glass, soda-lime glass, hard glass (Pyles glass), quartz, etc. used in liquid crystal display devices. Glass, polyethylene terephthalate, polybutylene terephthalate, polyethersulfone or polycarbonate, etc. The materials of the first conductive film 114 and the second conductive film 124 are selected from tin oxide (SnO ₂ ), indium oxide-tin oxide (In ₂ O ₃ —SnO ₂ ), and the like.

The first liquid crystal alignment film 116 and the second liquid crystal alignment film 126 are each the above-mentioned liquid crystal alignment film, and their function is to make the liquid crystal unit 130 form a pre-tilt angle. In addition, when a voltage is applied to the first conductive film 114 and the second conductive film 124 , an electric field may be generated between the first conductive film 114 and the second conductive film 124 . The electric field can drive the liquid crystal unit 130 , thereby changing the arrangement of the liquid crystal molecules in the liquid crystal unit 130 .

The present invention will be further described with reference to the following examples, but it should be understood that these examples are for illustrative purposes only, and should not be construed as limitations on the implementation of the present invention.

Preparation example of diamine compound (b-2)

Preparation Examples 1 to 4 of the diamine compound (b-2) are explained below:

Preparation Example 1

(1) Synthesis of compound (b-2-1b)

Add 1-fluoro-2,4-dinitro A solution of 29.84 g (160 mmol) of benzene (compound (b-2-1a)) in 60 g of tetrahydrofuran. After the dropwise addition, after confirming the completion of the reaction by high performance liquid chromatography (HPLC), 1 liter of dichloromethane was added and washed 3 times with 800 ml of distilled water. Next, the organic layer was dried using anhydrous magnesium sulfate, and after filtration, the solvent was distilled off with an evaporator. Finally, compound (b-2-1b) can be obtained after recrystallization using a co-solvent of 500 g of ethyl acetate/650 g of n-hexane.

(2) Synthesis of diamine compound (b-2-1)

In the presence of hydrogen, 19.28 g (72.7 mmol) of the aforementioned compound (b-2-1b), platinum (IV) oxide (PtO ₂ , water-containing type, 2.0 g, 10 wt %) and ethyl acetate were stirred at 40° C. A mixture of ester/ethanol 200 g (100/50 (v/v%)). After the reaction, the catalyst was filtered through celite, and the solvent was distilled off with an evaporator. Finally, using silica gel column chromatography (silica gel column chromatography), the mobile phase is n-hexane/ethyl acetate (100/50 (v/v%)) after purification, the diamine compound (b-2 -1).

Preparation example 2

(1) Synthesis of compound (b-2-2b)

At 23°C, in a mixture containing 44.38 grams (277 mmol) of 3-(2-aminoethyl) indole (3-(2-aminoethyl) indole), 29.12 grams (347 mmol) of sodium bicarbonate and 630 grams of distilled water In the mixed solution of 1-fluoro-2,4-dinitrobenzene (compound (b-2-2a) 43.00 g (231 mmol) of ethanol 840 g solution was added dropwise. After the addition was completed, it was confirmed by HPLC After the reaction was over, add 2 liters of dichloromethane and remove the water layer. Then, wash the organic layer 3 times with 500 ml of saturated brine, then use anhydrous magnesium sulfate to dry the organic layer, and distill with an evaporator after filtration Solvent. Finally, compound (b-2-2b) can be obtained after recrystallization using a co-solvent of 500 g of ethyl acetate/900 g of n-hexane.

(2) Synthesis of diamine compound (b-2-2)

In the presence of hydrogen, 3.56 g (10.9 mmol) of the compound (b-2-2b) obtained above, platinum (IV) oxide (PtO ₂ , aqueous type, 0.4 g, 10 wt%) and 1,4 - A mixture of dioxane 30 g. After the reaction, filter the catalyst with diatomaceous earth, and distill the solvent with an evaporator to obtain the diamine compound (b-2-2).

Preparation example 3

The compound represented by formula (b-2-3) (hereinafter referred to as "diamine compound (b-2-3)" was synthesized according to the following synthesis scheme 3.

(1) Synthesis of compound (b-2-3b)

Cool 300 g of tetrahydrofuran solution containing 29.92 g (277 mmol) of 3-(aminomethyl)pyridine (277 mmol) and 28.03 g (277 mmol) of triethylamine to below 10° C. While paying attention to heat generation, a solution of 150 g of tetrahydrofuran containing 60.76 g (263 mmol) of 3,5-dinitrobenzoyl chloride (compound (b-2-3a)) was added dropwise thereto. After completion of the dropwise addition, the reaction temperature was raised to 23° C., and the reaction was continued. Next, after confirming the completion of the reaction by HPLC, the reaction liquid was poured into 2 liters of distilled water, and the precipitated solid was filtered. Afterwards, after washing with water, disperse and wash with 450 g of ethanol to obtain compound (b-2-3b).

(2) Synthesis of diamine compound (b-2-3)

In the presence of hydrogen, 72.00 g (238 mmol) of the aforementioned compound (b-2-3b), 5% palladium-carbon (hydrous type, 7.2 g, 10 wt%) and 1,4-bis A mixture of oxane 720 g. After the reaction, the catalyst was filtered through celite, and the solvent was distilled off with an evaporator. Finally, the diamine compound (b-2-3) can be obtained after dispersing and washing with 360 g of ethanol.

Preparation Example 4

The compound represented by formula (b-2-4) (hereinafter referred to as "diamine compound (b-2-4)" was synthesized according to the following synthesis scheme 4.

(1) Synthesis of compound (b-2-4b)

In containing 1-(2-hydroxyethyl) pyrrole (1-(2-hydroxyethyl)pyrrole)) 35.67 g (321 mmol) and triethylamine 97.39 g (932 mmol) in tetrahydrofuran 240 g solution was added dropwise A solution of 29.84 g (160 mmol) of 1-fluoro-2,4-dinitrobenzene (compound (b-2-4a)) in 60 g of tetrahydrofuran. After the completion of the dropwise addition, the completion of the reaction was confirmed by HPLC, and dichloromethane was added 1 liter, and washed 3 times with 600 ml of distilled water. Then, dry the organic layer using anhydrous magnesium sulfate, and distill the solvent with an evaporator after filtration. Finally, use a co-solvent of 500 g of ethyl acetate/660 g of n-hexane to carry out After recrystallization, compound (b-2-4b) can be obtained.

(2) Synthesis of diamine compound (b-2-4)

In the presence of hydrogen, 20.15 g (72.7 mmol) of the aforementioned compound (b-2-4b), platinum (IV) oxide (PtO ₂ , aqueous type, 2.0 g, 10 wt %) and ethyl acetate were stirred at 40° C. A mixture of ester/ethanol 200 g (100/50 (v/v%)). After the reaction, the catalyst was filtered through celite, and the solvent was distilled off with an evaporator. Finally, using silica gel column chromatography (silica gel column chromatography), the mobile phase is n-hexane/ethyl acetate (100/50 (v/v%)) after purification, the diamine compound (b-2 -4).

Synthesis example of polymer (A)

Synthesis Example A-1-1 to Synthesis Example A-1-10 of the polymer (A) are described below:

Synthesis Example A-1-1

A nitrogen inlet, a stirrer, a condenser, and a thermometer were arranged on a four-necked conical flask with a volume of 500 milliliters, and nitrogen was introduced. Then, in a four-necked conical flask, add 0.60 gram (0.001 mol) of the diamine compound (abbreviated as b-1-1) represented by formula (1-10), 0.31 gram (0.0015 mol) of the obtained The diamine compound (abbreviated as b-2-1), 7.47 grams (0.015 moles) of the diamine compound represented by formula (3-1-3) (abbreviated as b-3-1), 3.50 grams (0.0325 moles ) of p-diaminobenzene (abbreviated as b-4-1) and 80 grams of N-methyl-2-pyrrolidone (abbreviated as NMP), and stirred at room temperature until dissolved. Next, 9.80 g (0.05 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (abbreviated as a-1) and 20 g of NMP were added and reacted at room temperature for 2 hours. After the reaction was finished, the reaction solution was poured into 1500 milliliters of water, so that the polymer was precipitated. Then, the obtained polymer was filtered, washed with methanol and filtered three times, placed in a vacuum oven, and dried at a temperature of 60° C. to obtain the polymer (A-1-1).

Synthesis Example A-1-2 to Synthesis Example A-1-10

Synthesis Example A-1-2 to Synthesis Example A-1-10 are the same steps as Synthesis Example A-1-1 to prepare polymer (A-1-2) to polymer (A-1-10) respectively , and its difference lies in: changing the type and usage amount of the monomer (as shown in Table 1).

Synthesis Example of Polymer

Synthesis Example A-2-1 to Synthesis Example A-2-5 of the polymer are described below:

Synthesis Example A-2-1

A nitrogen inlet, a stirrer, a condenser, and a thermometer were arranged on a four-necked conical flask with a volume of 500 milliliters, and nitrogen was introduced. Then, in a four-necked conical flask, add 0.60 gram (0.001 mol) of the diamine compound (abbreviated as b-1-1) represented by formula (1-10), 0.31 gram (0.0015 mol) of the obtained The diamine compound (abbreviated as b-2-1), 7.47 grams (0.015 moles) of the diamine compound represented by formula (3-1-3) (abbreviated as b-3-1), 3.50 grams (0.0325 moles ) of p-diaminobenzene (abbreviated as b-4-1) and 80 grams of N-methyl-2-pyrrolidone (abbreviated as NMP), and stirred at room temperature until dissolved. Next, 9.80 g (0.05 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (abbreviated as a-1) and 20 g of NMP were added. After reacting at room temperature for 6 hours, 97 g of NMP, 2.55 g of acetic anhydride, and 19.75 g of pyridine were added, the temperature was raised to 60° C., and stirring was continued for 2 hours to carry out imidization reaction. After the reaction was finished, the reaction solution was poured into 1500 milliliters of water, so that the polymer was precipitated. Then, the obtained polymer was filtered, washed with methanol and filtered three times, placed in a vacuum oven, and dried at a temperature of 60° C. to obtain the polymer (A-2-1).

Synthesis Example A-2-2 to Synthesis Example A-2-5

Synthesis Example A-2-2 to Synthesis Example A-2-5 are the same steps as Synthesis Example A-2-1 to prepare polymer (A-2-2) to polymer (A-2-5) respectively , and the difference lies in: changing the type and amount of monomer, catalyst and dehydrating agent (as shown in Table 2).

Comparative Synthesis Example A-3-1 to Comparative Synthesis Example A-3-7 of Polymers

Comparative synthesis example A-3-1 to comparison synthesis example A-3-7 is to prepare polymer (A-3-1) to polymer (A-3- 7), and its difference lies in: changing the kind of monomer and its usage amount (as shown in Table 3).

Comparative Synthesis Example A-3-8 to Comparative Synthesis Example A-3-11 of Polymers

Comparative synthesis example A-3-8 to comparison synthesis example A-3-11 is to prepare polymer (A-3-8) to polymer (A-3- 11), and the difference lies in: changing the type and amount of monomer, catalyst and dehydrating agent (as shown in Table 3).

The compounds corresponding to the symbols in Table 1, Table 2, and Table 3 are as follows.

Table 2

table 3

Table 3 (continued)

Examples and Comparative Examples of Liquid Crystal Alignment Agents, Liquid Crystal Alignment Films, and Liquid Crystal Display Elements

Examples 1 to 15 and Comparative Examples 1 to 11 of liquid crystal alignment agents, liquid crystal alignment films, and liquid crystal display elements are described below:

Example 1

a. Liquid crystal alignment agent

Weigh the polymer (A-1-1) of 100 weight parts, the N-methyl-2-pyrrolidone (abbreviated as B-1) of 1200 weight parts and the ethylene glycol n-butyl ether (abbreviated as B-1) of 600 weight parts -2), and at room temperature, continue to stir with a stirring device until dissolved, and the liquid crystal alignment agent of Example 1 can be formed.

b. Liquid crystal alignment film and liquid crystal display element

The liquid crystal alignment agent was coated on a glass substrate with a conductive film made of ITO by spin coating, and then pre-baked on a heating plate at a temperature of 100°C for 5 minutes, and in a circulating oven at a temperature of Post-bake at 220°C for 30 minutes to obtain a coating film.

Using a Hg-Xe lamp and a Glan-Taylor prism (Glan-Taylor prism), irradiate the surface of the coating film with polarized ultraviolet light containing a 313nm bright line for 50 seconds from a direction inclined 45° from the normal line of the substrate to impart liquid crystal alignment To make a liquid crystal alignment film. At this time, the illuminance of the irradiated surface at a wavelength of 313 nm was 2 mW/cm ² . The same operation was repeated to produce two substrates (one pair) having a coating film (liquid crystal alignment film) subjected to polarized ultraviolet irradiation treatment.

Next, by screen printing, an epoxy resin adhesive containing alumina balls with a diameter of 5.5 μm was applied to the outer periphery of the surface on which the liquid crystal alignment film was formed on the pair of substrates, so that the liquid crystals on each substrate were aligned. The film faces are facing each other, and the irradiation direction of the polarized ultraviolet rays is antiparallel to the substrate, and then the hot press is applied with a pressure of 10kg, and the hot pressing is carried out at 150°C.

After that, the liquid crystal is injected from the liquid crystal injection port, and then the liquid crystal injection port is sealed with an epoxy resin adhesive. In order to eliminate the flow alignment during liquid crystal injection, it was heated to 150°C and then slowly cooled to room temperature. Finally, the polarizing plates were bonded on both outer sides of the substrate so that their polarization directions were perpendicular to each other and 45° to the ultraviolet polarization direction of the liquid crystal alignment film, to obtain the liquid crystal display element of Example 1.

Table 4 shows the results of evaluating the liquid crystal display element of Example 1 by each evaluation method described later.

Example 2 to Example 15

The liquid crystal alignment agents, liquid crystal alignment films, and liquid crystal display elements of Examples 2 to 15 were prepared in the same steps as in Example 1, and the difference is that the types and amounts of ingredients were changed, as shown in Table 4. Show. The liquid crystal display elements prepared in Examples 2 to 15 were evaluated in the following evaluation manner, and the results are shown in Table 4.

Comparative Example 1 to Comparative Example 11

The liquid crystal alignment agents, liquid crystal alignment films, and liquid crystal display elements of Comparative Example 1 to Comparative Example 11 were prepared in the same steps as in Example 1, except that the types and usage amounts of the ingredients were changed, as shown in Table 5 . The liquid crystal display elements prepared in Comparative Example 1 to Comparative Example 11 were evaluated in the following evaluation manner, and the results are shown in Table 5.

The compounds corresponding to the symbols in Table 4 and Table 5 are as follows.

Evaluation method

UV reliability

The ultraviolet reliability of the liquid crystal alignment film is evaluated by the voltage retention rate of the liquid crystal display element. Furthermore, the measurement method of the voltage holding ratio of a liquid crystal display element is as follows.

The voltage holding ratios of the liquid crystal display elements of the examples and the comparative examples were respectively measured using an electrical measuring machine (manufactured by Toyo Corporation, Model 6254). The test condition is to apply a voltage of 4 volts, release the voltage after 2 milliseconds, and measure the voltage retention rate (referred to as VHR1) after 1667 milliseconds from the release. Next, after irradiating the liquid crystal display element with 4200mJ/ ^cm2 of ultraviolet light (the model of the ultraviolet light irradiation machine is KN-SH48K1; manufactured by Guangneng Xingye), measure the voltage retention rate (meter) after the ultraviolet light irradiation with the same test conditions. for VHR2). Finally, the percentage change of the voltage retention rate (calculated as VHRUV (%)) can be obtained by calculating with formula (7). A lower percentage change in voltage retention indicates better UV reliability.

Formula (7)

The evaluation criteria for the percentage change in the voltage retention rate are as follows.

※: VHR ^UV <4%

◎: 4%≦VHR ^UV <5%

○: 5%≦VHR ^UV <10%

△: 10%≦VHR ^UV <20%

╳: 20%≦VHR ^UV

Table 4

Table 4 (continued)

table 5

Table 5 (continued)

<Evaluation result>

As can be seen from Table 4 and Table 5, the polymer ( A) Compared with the formed liquid crystal alignment film (Comparative Example 1 to Comparative Example 11), the diamine compound (b-1), the diamine compound (b-2) and the diamine compound (b-3) were used at the same time. The UV reliability of the liquid crystal alignment film (Example 1 to Example 15) is better.

In addition, when a diamine compound (b-2) selected from pyrrolyl, imidazolyl, pyrazolyl, pyridyl or pyrimidyl is used in the polymer (A), the formed liquid crystal alignment film (Example 3, 4, 5, 7, 8, 9, 10, 13, 15) have better UV reliability.

In addition, when the polymer (A) in the liquid crystal alignment agent contains the diamine compound (b-4) represented by formula (II-1), formula (II-2), formula (II-26) to formula (II-30) , the UV reliability of the formed liquid crystal alignment film (Example 3, 4, 9, 13) is particularly good.

In summary, the polymer in the liquid crystal alignment agent of the present invention is formed by the tetracarboxylic dianhydride component and the diamine component containing the diamine compound of a specific structure, so the liquid crystal alignment agent is applied to the liquid crystal alignment film , the liquid crystal alignment film has better ultraviolet reliability, and thus is suitable for liquid crystal display elements.

Although the present invention has been disclosed as above with the embodiments, it is not intended to limit the present invention. Anyone with ordinary knowledge in the technical field can make some changes and modifications without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention should be defined by the scope of the appended patent application.

Claims (9)

1. A liquid crystal alignment agent, characterized in that, comprising: polymer (A); and solvent (B), Wherein, the polymer (A) is obtained by the reaction of a mixture, and the mixture includes a tetracarboxylic dianhydride component (a) and a diamine component (b), The diamine component (b) is composed of a diamine compound (b-1) represented by the formula (1), a diamine compound (b-2) represented by the formula (2), a Structure of the diamine compound (b-3) and other diamine compounds (b-4) composition, In the mixture (A), based on the total usage amount of the diamine component (b) being 100 moles, the usage amount of the tetracarboxylic dianhydride component (a) is 20 moles to 200 moles, and Based on the usage amount of the diamine component (b) being 100 moles, the usage amount of the diamine compound (b-1) represented by the formula (1) is 0.3 moles to 10 moles, and the usage amount represented by the formula (2 ) is used in an amount of 0.3 moles to 10 moles of the diamine compound (b-2), and the amount of the diamine compound (b-3) represented by the formula (3) is used in an amount of 5 moles to 90 moles , the usage amount of the diamine compound (b-4) is 0 moles to 94 moles, In formula (1), Y represents an alkylene group with a carbon number of ¹ to 12; Y represents a group having a steroid skeleton or a group represented by ^formula (1-1), In formula (1-1), R ¹ each independently represent a fluorine atom or a methyl group; R ² represents a hydrogen atom, a fluorine atom, an alkyl group with 1 to 12 carbons, a fluoroalkyl group with 1 to 12 carbons, an alkoxy group with 1 to 12 carbons, -OCH ₂ F, -OCHF ₂ or -OCF ₃ ; Z ¹ , Z ² and Z ³ each independently represent a single bond, an alkylene group having 1 to 3 carbon atoms, -O-, Z ⁴ are independently indicated R ^a and R ^b each independently represent a fluorine atom or a methyl group, h and i each independently represent 0, 1 or 2; a represents 0, 1 or 2; b, c and d each independently represent an integer from 0 to 4; e, f and g each independently represent an integer from 0 to 3, and e+f+g≧1; In formula (2), ^Y3 each independently represents -O-, -NH-, -CH ₂ O-, Y ⁴ each independently represent a single bond, a divalent aliphatic hydrocarbon group with a carbon number of 1 to 20, a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group; Y ⁵ each independently represent a single bond, -O-, -NH-, Where m represents an integer from 1 to 5; Y ⁶ each independently represent a nitrogen-containing aromatic heterocyclic group; j represents an integer from 1 to 4; In formula (3), R ³ and R ⁴ each independently represent an alkyl group with 1 to 6 carbons, an alkoxy group with 1 to 6 carbons, a halogen atom or a cyano group; n1 and n2 each independently represent an integer from 0 to 4; n3 represents an integer of 0 or 1; * Each independently indicates the bonding position. 2. The liquid crystal alignment agent according to claim 1, wherein, in the formula (2), Y ³ each independently represent -O-, -NH-, -CH ₂ O-, 3. The liquid crystal alignment agent according to claim 1, wherein, in the formula (2), Y ⁴ each independently represent a single bond, an alkylene group or a phenylene group with a carbon number of 1 to 5. 4. The liquid crystal alignment agent according to claim 1, wherein, in the formula (2), Y ⁵ each independently represent a single bond, -O-, wherein m represents an integer of 1 to 5. 5. The liquid crystal alignment agent according to claim 1, wherein, in the formula (2), Y ⁶ each independently represent pyrrolyl, imidazolyl, pyrazolyl, pyridyl or pyrimidinyl. 6. The liquid crystal alignment agent according to claim 1, wherein, in the formula (2), j represents an integer of 1 to 3. 7. The liquid crystal alignment agent according to claim 1, wherein the diamine compound (b-3) is composed of a structure represented by formula (3-1) and a structure represented by formula (3-2) at least one of the group of In formula (3-1) and formula (3-2), R ³ and R ⁴ each independently represent an alkyl group with 1 to 6 carbons, an alkoxy group with 1 to 6 carbons, a halogen atom or a cyano group; R ⁵ and R ⁶ each independently represent an alkyl group with 1 to 40 carbons or an alkyl group with 1 to 40 carbons substituted by a fluorine atom; W ¹ , W ² and W ³ each independently represent -O-, Wherein R ⁷ represents a hydrogen atom or an alkyl group with a carbon number of 1 to 4; X ¹ and X ² each independently represent a methylene group, an aryl group, a divalent alicyclic group, -Si(CH ₃ ) ₂ -, -CH=CH-, -C≡C-, and a substituted methylene group , an aryl group with a substituent, a divalent alicyclic group with a substituent, -Si(CH ₃ ) ₂ - with a substituent, -CH=CH- with a substituent, wherein the substituent is a cyano group , a halogen atom or an alkyl group with 1 to 4 carbon atoms; n1 and n2 each independently represent an integer from 0 to 4; n3 represents an integer of 0 or 1; n4 and n7 independently represent an integer from 1 to 6; n5 and n8 each independently represent an integer from 0 to 2; n6 means 0 or 1; * Each independently indicates the bonding position. 8. A liquid crystal alignment film, characterized in that it is formed from the liquid crystal alignment agent according to any one of claims 1-7. 9. A liquid crystal display element, characterized in that it comprises the liquid crystal alignment film as claimed in claim 8.